In-situ alkylphenol-aldehyde resins

ABSTRACT

The invention relates to an in-situ process for preparing an alkylphenol-aldehyde resin. The process comprises the step of providing a raw alkylphenol composition. The raw alkylphenol composition comprises one or more alkylphenol compounds and at least about 1 wt % phenol. Each alkylphenol compound has one or more alkyl substituents. The raw alkylphenol composition is reacted directly, without pre-purification, with one or more aldehydes to form an in-situ alkylphenol-aldehyde resin. The invention also relates to an in-situ alkylphenol-aldehyde resin formed from the in-situ process, and its use in a tackifier composition and rubber composition. The tackifier composition and rubber composition containing the in-situ alkylphenol-aldehyde resin show, inter alia, improved tack performance.

This application claims the benefit of priority of U.S. ProvisionalPatent Application Ser. No. 61/892,213, filed Oct. 17, 2013, which ishereby incorporated by reference in its entirety.

FIELD OF THE INVENTION

This invention generally relates to an in-situ process for preparing analkylphenol-aldehyde resin and tackifier compositions and rubbercompositions containing the alkylphenol-aldehyde resin formed from thein-situ process. The tackifier compositions and rubber compositionscontaining the alkylphenol-aldehyde resin prepared from the in-situprocess show, inter alia, improved tack performance.

BACKGROUND

Rubber products are frequently made up of several rubber layers eachwith a same or a different chemical composition. During this “build up,”the rubber layers must adhere to one another adequately in theirpre-vulcanized state. For example, an assembled tire blank is requiredto hold together for a fairly long period prior to vulcanization. It istherefore important that the rubber mixtures used have an adequate“tack,” the force required to pull apart two pre-vulcanized rubbermixtures which have been pressed together under certain definedconditions. While natural rubber mixtures generally have good tackiness,mixtures of synthetic rubbers are much less tacky and, in extreme cases,possess no tackiness at all. Therefore, it has been common practice toadd a tackifier to less tacky rubbers or rubber mixtures to increasetheir tack. In synthetic rubber products, synthetic rubber adhesivecompositions are employed to improve tack and provide good curedadhesion. Moreover, the rubber composition must not only have goodinitial tack, but also remain sufficiently tacky during themanufacturing process (i.e., good tack retention), even when the processis interrupted for fairly long periods, which is not unusual,particularly when manufacturing involves processes at differentlocations or requires storage and/or transport of pre-finished goods.

To ensure adequate tack, conventional methods of preparingalkylphenol-aldehyde resins typically use high-purity alkylphenols(e.g., commercially available resin-grade alkylphenols having a puritylevel of higher than about 98 wt %). However, using a purifiedalkylphenol is expensive and can significantly increased processing timeand manufacturing costs.

Therefore, there remains a need to develop tackifiers which provideincreased tack and tack retention, and, at the same time, also provide acost-effective and time-efficient solution. A particular need exists inthe tire industry because of the poor tack and tack retention ofsynthetic rubber compositions, such as commercial SBR-based tirecompositions. This invention answers that need.

SUMMARY OF THE INVENTION

One aspect of the invention relates to an in-situ process for preparingan alkylphenol-aldehyde resin. The process comprises the step ofproviding a raw alkylphenol composition. The raw alkylphenol compositioncomprises one or more alkylphenol compounds and at least about 1 wt %phenol. Each alkylphenol compound has one or more alkyl substituents.The raw alkylphenol composition is reacted directly, withoutpre-purification, with one or more aldehydes to form an in-situalkylphenol-aldehyde resin.

Another aspect of the invention relates to an alkylphenol-aldehyde resinprepared by reacting, without pre-purification, a raw alkylphenolcomposition directly with one or more aldehydes. The raw alkylphenolsource comprises one or more alkylphenol compounds and at least about 1wt % phenol. Each alkylphenol compound has one or more alkylsubstituents.

Another aspect of this invention relates to a tackifier compositioncomprising the alkylphenol-aldehyde resin prepared by reacting, withoutpre-purification, a raw alkylphenol composition directly with one ormore aldehydes. The raw alkylphenol source comprises one or morealkylphenol compounds and at least about 1 wt % phenol. Each alkylphenolcompound has one or more alkyl substituents. The tackifier compositionhas improved tack performance, when used in a rubber composition.

Another aspect of this invention relates to a rubber compositioncomprising the alkylphenol-aldehyde resin prepared by reacting, withoutpre-purification, a raw alkylphenol composition directly with one ormore aldehydes. The raw alkylphenol source comprises one or morealkylphenol compounds and at least about 1 wt % phenol. Each alkylphenolcompound has one or more alkyl substituents. The rubber composition hasimproved tack performance.

Additional aspects, advantages and features of the invention are setforth in this specification, and in part will become apparent to thoseskilled in the art on examination of the following, or may be learned bypractice of the invention. The inventions disclosed in this applicationare not limited to any particular set of or combination of aspects,advantages and features. It is contemplated that various combinations ofthe stated aspects, advantages and features make up the inventionsdisclosed in this application.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the tack performance (tack and tack retention) of therubber blends using the mixed in-situ resin prepared from a mixture ofin-situ PTBP and in-situ PTOP (Resin ii-1), as compared to the tackperformance of the rubber blends using in-situ PTOP resin (Resini-PTOP), and the tack performance of the rubber blends using resinsprepared from a mixture of in-situ PTOP and resin-grade PTBP (Resinir-1).

FIG. 2 shows the tack performance (tack and tack retention) of therubber blends using the two in-situ PTBP resins having different meltingpoints (Resin i-PTBP-1 and Resin i-PTBP-2), as compared to the tackperformance of the rubber blends using corresponding resin-grade PTBPresin (Resin r-PTBP-1 and Resin r-PTBP-2), and the tack performance ofthe rubber blends using resins prepared from a mixture of in-situ PTOPand in-situ PTBP (Resin ii-1).

FIG. 3 shows the results of tack and tack retention of rubber blendsusing an in-situ resin prepared from in-situ PTBP with an aminemodification and a salicylic-acid stabilization (Resin i-PTBP-amine-SA),as compared to the tack and tack retention of the rubber blends usingin-situ PTBP resins with a lower melting point (Resin i-PTBP-1), and thetack and tack retention of the rubber blends using resin-grade PTBPresin with a lower melting point (Resin r-PTBP-1).

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to an in-situ process for preparing analkylphenol-aldehyde resin, and tackifier compositions and rubbercompositions containing the alkylphenol-aldehyde resin formed from thein-situ process. The in-situ process uses a raw alkylphenol compositionand eliminates the need for a pre-purification of alkylphenol beforereacting with an aldehyde. The resulting in-situ alkylphenol-aldehyderesin, when used in a tackifier composition, possesses a consistentlyimproved tack and tack retention compared to a regularalkylphenol-aldehyde resin prepared from a purified alkylphenol.

In-Situ Preparation of an Alkylphenol-Aldehyde Resin

One aspect of the invention relates to an in-situ process for preparingan alkylphenol-aldehyde resin. The process comprises the step ofproviding a raw alkylphenol composition. The raw alkylphenol compositioncomprises one or more alkylphenol compounds and at least about 1 wt %phenol. Each alkylphenol compound has one or more alkyl substituents.The raw alkylphenol composition is reacted directly, withoutpre-purification, with one or more aldehydes to form an in-situalkylphenol-aldehyde resin.

Suitable alkylphenol compounds for preparing the in-situalkylphenol-aldehyde resin may have one or more alkyl groups in theortho, meta, and/or para positions of the phenol. The alkyl group of thealkylphenol compounds may be a linear, branched, or cyclic alkylcontaining 1 to 30 carbon atoms. Typically, the alkyl group contains 4to 18 carbon atoms. Typical alkylphenol compositions includes at leastone main alkylphenol component having at least one alkyl group at thepara position of the phenol. Exemplary alkylphenols includepara-methylphenol, para-tert-butylphenol (PTBP), para-sec-butylphenol,para-tert-hexylphenol, para-cyclohexylphenol, para-tert-octylphenol(PTOP), para-isooctylphenol, para-decylphenol, para-dodecylphenol,para-tetradecyl phenol, para-octadecylphenol, para-nonylphenol,para-pentadecylphenol, and para-cetylphenol.

The alkylphenol composition can be prepared in any suitable manner knownin the art. One way to prepare the alkylphenol composition is throughalkylation of phenol by directly reacting phenol with an alkylene.Various other methods of producing alkylphenol, including tert-butylphenols, are disclosed in U.S. Pat. No. 4,166,191 and WO 2011/069052,which are hereby incorporated by reference in their entirety.Alternatively, the alkylphenol composition may be prepared bytransalkylation of a crude alkylphenol with phenol. Varioustransalkylation reactions are disclosed in U.S. Pat. No. 5,399,786,which is hereby incorporated by reference in its entirety. Using thetransalkylation of crude alkylphenol, a crude or residual alkylphenolcan be recycled or recovered easily and reused directly as a reactionmaterial for the in-situ process. This is particularly advantageous inthe in-situ process, as the process does not require a pre-purificationstep for the alkylphenol composition before it is reacted with analdehyde. Thus, this in-situ process promotes a cost-effective way inre-using alkylphenol crude.

Regardless the method used to prepare the alkylphenol composition, theraw alkylphenol composition, without further purification, contains someamount of impurity (more than a trace amount). It includes unreactedphenol and one or more side-product alkylphenols where the number of thealkyl groups on phenol varies, and/or where alkyl groups are atdifferent positions of phenol, and/or where alkyl groups are indifferent isomeric forms. For instance, raw PTBP prepared by reactingisobutylene and phenol is typically a mixture containing not only PTBP,but also di-tert-butylphenol (e.g., 2,4-di-tert-butylphenol or2,6-di-tert-butylphenol) and unreacted phenol, and may additionallycontain ortho-tertbutylphenol and tri-tert-butylphenol (e.g.,2,4,6-tri-tert-butylphenol). For instance, raw PTOP prepared by reactingoctene (e.g., diisobutylene) and phenol is typically a mixturecontaining not only PTOP, but also di-tert-octylphenol (e.g.,2,4-di-tert-octylphenol or 2,6-di-tert-octylphenol) and unreactedphenol, and may additionally contain ortho-tert-octylphenol andtri-tert-octylphenol (e.g., 2,4,6-tri-tert-octylphenol).

Conventional technology for preparing alkylphenol-aldehyde resintypically uses commercially available high-purity alkylphenol (e.g.,resin-grade), or, if the alkylphenol compound is prepared directly fromthe olefin and phenol, it requires that the alkylphenol be distilledfrom the product mixture to obtain a purified alkylphenol before furtherusage. Typically, a high-purity alkylphenol composition (e.g.,commercially available resin-grade) contains at least about 98 wt % orat least about 99 wt % the main alkylphenol component, and less thanabout 2 wt % or less than about 1 wt % phenol. For example, commerciallyavailable resin-grade PTBP contains at least 99.9 wt % PTBP and lessthan 0.1 wt % phenol; commercially available resin-grade PTOP containsat least 98 wt % PTOP and less than 2 wt % phenol.

The embodiments of the invention, however, require the use of an in-situalkylphenol composition (i.e., a raw alkylphenol composition prepared,without further processing to obtain a purified alkylphenol component)to react directly with one or more aldehydes to form an in-situalkylphenol-aldehyde resin. This process is also referred to as an“in-situ” preparation of alkylphenol-aldehyde resin. The raw, unpurifiedalkylphenol composition is referred to as an “in-situ” alkylphenolcomposition. The alkylphenol-aldehyde resin prepared by such in-situalkylphenol composition and in-situ process is referred to as an“in-situ” alkylphenol-aldehyde resin.

The in-situ process uses a raw alkylphenol composition, and eliminates,or substantially reduces, the pre-purification of alkylphenol beforefurther usage. When the raw alkylphenol composition contains one mainalkylphenol component, this main alkylphenol component may be as low asabout 50 wt %. For instance, the main alkylphenol component may rangefrom about 50 wt % to about 99 wt %, from about 50 wt % to about 95 wt%, from about 50 wt % to about 90 wt %, from 50 wt % to about 85 wt %,or from about 75 wt % to about 85 wt %. The raw alkylphenol compositionmay contain at least about 1 wt % phenol. For instance, phenol may rangefrom about 1 wt % to about 10 wt %, about 2 wt % to about 10 wt %, about3 wt % to about 10 wt %, about 4 wt % to about 10 wt %, about 5 wt % toabout 10 wt %, or about 6 wt % to about 8 wt %. The other side productalkylphenols may range from 0 to about 50 wt %, from about 5 wt % toabout 50 wt %, for instance from about 7 wt % to about 18 wt %.

In one embodiment, the main alkylphenol component contained in thein-situ alkylphenol composition is PTBP. The in-situ alkylphenolcomposition comprises PTBP, phenol, di-tert-butylphenol, and optionallytri-tert-butylphenol and ortho-tert-butylphenol. In this in-situ PTBPcomposition, PTBP may range from about 50 wt % to about 99 wt % or fromabout 50 wt % to about 85 wt %, phenol may range from about 1 wt % toabout 10 wt % or from about 5 wt % to about 10 wt %, di-tert-butylphenolmay range from 0 to about 14 wt % or from about 7 wt % to about 14 wt %,ortho-tert-butylphenol may range from 0 to about 3 wt %, andtri-tert-butylphenol may range from 0 to about 1 wt %.

In one embodiment, the main alkylphenol component contained in thein-situ alkylphenol composition is PTOP. The in-situ alkylphenolcomposition comprises PTOP, phenol, di-tert-octylphenol, and optionallyortho-tert-octylphenol and tri-tert-octylphenol. In this in-situ PTOPcomposition, PTOP may range from about 50 wt % to about 99 wt % or fromabout 50 wt % to about 85 wt %, phenol may range from about 1 wt % toabout 10 wt % or from about 5 wt % to about 10 wt %, di-tert-octylphenolmay range from 0 to about 14 wt % or from about 7 wt % to about 14 wt %,ortho-tert-octylphenol may range from 0 to about 3 wt %, andtri-tert-octylphenol may range from 0 to about 1 wt %.

The in-situ process can also use a mixture of two or more differentin-situ alkylphenol compositions, e.g., mixture of one raw alkylphenolcomposition (e.g., its main alkylphenol component is alkylphenol-1) andanother raw alkylphenol composition (e.g., its main alkylphenolcomponent is alkylphenol-2, wherein alkylphenol-2 is different fromalkylphenol-1). Exemplary in-situ alkylphenol composition for preparingan alkylphenol-aldehyde resin includes a mixture of an in-situ PTBPcomposition and an in-situ PTOP composition. The ratio of the differentin-situ alkylphenol compositions in the mixture can vary. For example,the ratio of in-situ PTBP to in-situ PTOP in a mixture can range fromabout 90:10 to about 10:90, from about 75:25 to about 25:75, from about60:40 to about 40:60, from about 60:40 to about 50:50. An exemplaryratio of in-situ PTBP to in-situ PTOP in a mixture is about 58:42. Theweight percentage ranges of the two or more main alkylphenol components,phenol, and other side-product alkylphenols in the mixture of thein-situ alkylphenol compositions can be proportionated from the ratiosof the different in-situ alkylphenol compositions in the mixture.

The mixture of different in-situ alkylphenol compositions can beprepared by preparing different in-situ alkylphenol compositionsseparately and then mix them together. Alternatively, the mixture ofdifferent in-situ alkylphenol compositions can be prepared in a one-potprocess. In this one-pot process, a mixture of different in-situalkylphenol compositions can be prepared by reacting phenol with a firstalkyl compound to form the first in-situ alkylphenol, and subsequentlyadding a second alkyl compound to form the second in-situ alkylphenol;different alkyl compounds can be subsequently added into the existingmixture of in-situ alkylphenol composition in this one-pot process, ifadditional in-situ alkylphenols are desired in the mixture. The sequenceof adding different alkyl compounds can change. For example, a mixtureof in-situ PTBP and in-situ PTOP can be prepared by one-pot synthesis byreacting phenol with isobutylene first to produce in-situ PTBP, and thenadding diisobutylene into the reaction mixture to additionally producein-situ PTOP, or vise versa. The additions of alkyl compounds can alsobe simultaneous rather than sequential, i.e., when preparing the mixtureof different in-situ alkylphenol compositions in the one-pot process,two or more different alkyl compounds or all different alkyl compoundscan be added simultaneously.

The in-situ process can also use a mixture of an in-situ alkylphenolcomposition and a purified alkylphenol composition to prepare in-situalkylphenol-aldehyde resins. The in-situ alkylphenol composition maycontain a same or different main alkylphenol component than the purifiedalkylphenol composition. Exemplary in-situ alkylphenol composition forpreparing an alkylphenol-aldehyde resin includes a mixture of an in-situPTBP composition and a purified PTOP composition, or a mixture of anin-situ PTOP composition and a purified PTBP composition.

After the in-situ alkylphenol composition is obtained, it is thendirectly reacted, without purification, with one or more aldehydes togenerate an in-situ alkylphenol-aldehyde resin. Without being bound bytheory, the in-situ alkylphenol composition containing a mixture ofside-product alkylphenols that promote the incorporation of morealdehyde into the alkylphenol-aldehyde resin and can increase themolecular weight of the formed alkylphenol-aldehyde resin, resulting ahigher melt point which typically contributes to a better tackperformance when the resin is used in a tack composition. Increased tackperformance herein can refer to initial tack, long term (aged) tack (ortack retention), or both. The improvement in aged tack (or tackretention) of a tackifier composition or rubber composition isparticularly desirable, as it is often required that the tackifiercomposition remain sufficiently tacky over a fairly long period; it isnot unusual that manufacture processes of goods containing the tackifiercomposition to be interrupted for fairly long periods when involvingprocesses at different locations or involving storage and/ortransportation of pre-finished goods. Moreover, the need for additionaladhesive compositions to improve tack retention can be eliminated whenusing the in-situ alkylphenol-aldehyde resin, thereby reducing cost.

The tack of the formed in-situ alkylphenol-aldehyde resin, when used ina rubber composition, typically can increase about 10% or more, about30% or more, about 50% or more, about 60% or more, about 200% or more,about 300% or more, about 500% or more, or about 800% or more, comparedto an alkylphenol-aldehyde resin prepared from a purified alkylphenol.For instance, FIG. 2 shows that the tack of the formed in-situalkylphenol-aldehyde resin in a rubber composition can increase about30% or more (Resin i-PTBP-1 v. Resin r-PTBP-1 at Day 1), or about 800%or more (Resin i-PTBP-2 v. Resin r-PTBP-2 at Day 1).

The tack retention of the formed in-situ alkylphenol-aldehyde resin,when used in a rubber composition, typically can increase about 40% ormore, about 60% or more, about 120% or more, about 200% or more, about300% or more, about 500% or more, or about 600% or more, compared to analkylphenol-aldehyde resin prepared from a purified alkylphenol. Forinstance, FIG. 2 shows that the tack retention (after 3 days or 8 days)of the formed in-situ alkylphenol-aldehyde resin in a rubber compositioncan increase about 60% or more (Resin i-PTBP-1 v. Resin r-PTBP-1 at Day3), about 120% or more (Resin i-PTBP-2 v. Resin r-PTBP-2 at Day 8),about 400% or more (Resin i-PTBP-1 v. Resin r-PTBP-1 at Day 8), or about600% or more (Resin i-PTBP-1 v. Resin r-PTBP-1 at Day 3).

The tack performance comparisons of the in-situ alkylphenol-aldehyderesins with regular alkylphenol-aldehyde resins are made keeping allconditions or compositions the same, or substantially the same, exceptthat the regular alkylphenol-aldehyde resin is prepared from a purifiedalkylphenol. The purified alkylphenol used in the comparisons typicallyrefers to a high-purity alkylphenol composition (e.g., commerciallyavailable resin-grade) containing at least about 98 wt % or at leastabout 99 wt % the main alkylphenol component, and less than about 2 wt %or less than about 1 wt % phenol. For example, commercially availableresin-grade PTBP contains at least 99.9 wt % PTBP and less than 0.1 wt %phenol; commercially available resin-grade PTOP contains at least 98 wt% PTOP and less than 2 wt % phenol.

The in-situ alklyphenol-aldehyde resins prepared from a mixture ofdifferent in-situ alkylphenol compositions have also shown better tackand tack retention, when used in a rubber composition, than a regularalklyphenol-aldehyde resin prepared from a mixture of purifiedalkylphenol compositions or a mixture of purified alkylphenolcomposition and in-situ alkylphenol composition. For instance, FIG. 1shows that the tack retention of the formed mixture of in-situalkylphenol-aldehyde resin, when used in a rubber composition, canincrease about 90% or more (Resin ii-1 v. Resin ir-1 at Day 8), or about150% or more (Resin ii-1 v. Resin ir-1 at Day 3) than analklyphenol-aldehyde resin prepared from a mixture of purifiedalkylphenol composition and in-situ alkylphenol composition.

Any aldehyde known in the art for preparing an alkylphenol-aldehyderesin is suitable in the in-situ process. Exemplary aldehydes includeformaldehyde, methylformcel, butylformcel, acetaldehyde, propionaldehde,butyraldehyde, crotonaldehyde, valeraldehyde, caproaldehyde,heptaldehyde, benzaldehyde, as well as compounds that decompose toaldehyde such as paraformaldehyde, trioxane, furfural,hexamethylenetriamine, aldol, β-hydroxybutyraldelhyde, and acetals, andmixtures thereof. A typical aldehyde used is formaldehyde.

The reaction of alkylphenols with aldehyde to preparealkylphenol-aldehyde resins is known in the art. The type of catalystand the molar ratio of the reactants used in reaction determines themolecular structure and physical properties of the resins. A typicalacid catalyst used is p-toluene sulfonic acid or dodecylbenzensulfonicacid. An aldehyde:phenol ratio between 0.5:1 and 1:0.1 (typically 0.5:1to 0.8:1) with an acid catalyst typically generates novolak resins,which are thermoplastic in character. A higher aldehyde:phenol ratio(e.g., more than 1:1 to 3:1) with a basic catalyst typically give riseto resole resins, which are characterized by their ability to bethermally hardened at elevated temperatures.

The process of reacting an in-situ alkylphenol composition with one ormore aldehydes can be used to prepare novolak resins, following anysuitable process for preparing novolak resins known in the art. Forinstance, an in-situ alkylphenol composition can be directly reacted,without pre-purification, with one or more aldehydes in the presence ofa catalyst (e.g. an acid catalyst) to form a novolak resin. Anadditional aldehyde may be added later before the final product isneutralized to adjust the desirable melt point of the resin. Suitableacid catalysts for preparing novolak resins include ethanesulfonic acid,benzenesulfonic acid, benzenedisulfonic acid, chlorobenzenesulfonicacid, 3,4-dichlorobenzene sulfonic acid, cresolsulfonic acids, phenolsulfonic acids, toluenesulfonic acids, xylenesulfonic acids,octylphenolsulfonic acid, naphthalenesulfonic acid,1-naphthol-4-sulfonic acid, dodecylsulfonic acid, dodecylbenzensulfonicacid, and oxalic acid. A further description of the process forpreparing novolak resins can be found in U.S. Pat. Nos. 8,030,418 and8,470,930, which are hereby incorporated by reference in their entirety.

The process of reacting an in-situ alkylphenol composition with analdehyde can also be used to prepare resole resins, following anysuitable process for preparing resole resins known in the art. Forinstance, an in-situ alkylphenol composition can be directly reacted,without pre-purification, with one or more aldehydes in the presence ofa base, as a basic catalyst, or for base modification of the resultingresins. Suitable bases for preparing resole resins include ammoniumhydroxide; tertiary amines such as triethylamine, triethanolamine,diethyl cyclohexyl amine, triisobutyl amine; and alkali and alkalineearth metal oxides and hydroxides. Alternatively, an in-situ alkylphenolcomposition can be directly reacted, without pre-purification, with oneor more aldehydes in the presence of an acid catalyst to form a novolakresin first. Then, the novolak resin can be further reacted with one ormore aldehydes under basic conditions to form a resole resin.

The resulting in-situ alkylphenol-aldehyde resins can be modified withone or more bases. Suitable bases are typically primary or secondaryamines having a formula of NHR′R″, wherein R′ and R″ are independentlyH, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, aryl, hydroxyl C₁-C₆alkyl, carboxy C₁-C₆ alkyl, or R′ and R″ together form a 5- to7-membered nitrogenous heterocyclic ring. Exemplary amines include monoand di-amino alkanes and their substituted analogs, e.g., ethylamine,dimethylamine, dimethylaminopropyl amine and diethanol amine; arylamines and diamines, e.g., aniline, naphthylamine, benzyl amine,phenylene diamine, diamino naphthalenes; heterocyclic amines, e.g.,morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine, andpiperidine; melamine and their substituted analogs. Other representativeamines are alkylene polyamine, including ethylene polyamines which canbe formed from reactants such as ethylenediamine, diethylene triamine,triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine,hexaethylene heptamine, heptaethylene octamine, octaethylene nonamine,nonaethylene decamine, decaethylene undecamine and mixtures of suchamines having nitrogen contents corresponding to the alkylenepolyamines; and propylene polyamines which can be formed from reactantssuch as propylene diamine and di-, tri-, tetra-, penta-propylene tri-,tetra-, penta-, and hexa-amines. A further description of the processfor preparing base-modified alklyphenol-aldehyde resins can be found inU.S. Pat. No. 8,030,418, which is hereby incorporated by reference inits entirety. A typical base used is morpholine.

To allow adequate reaction of the in-situ alkylphenol composition withone or more aldehydes, xylene can be added in the reaction system, in asmall amount, to keep the viscosity of the reaction mixture low and tokeep the reaction product at a lower temperature until neutralizationcan be conducted. Other aliphatic (including cycloaliphatic) oraromatic, non-reactive organic solvent that has low-viscosity can alsobe used, such as toluene, benzene, naphthalene, nonane, octane,petroleum fractions, and the like.

After the in-situ alkylphenol-aldehyde resins are modified with one ormore bases, the base-modified alkylphenol-aldehyde resin can be furtherreacted with an epoxide or other chemical reagents to stabilize thebasic moiety or other reactive moieties in the modified resin. Adetailed process for stabilizing a base-modified alkylphenol-aldehyderesin with an epoxide can be found in U.S. Pat. No. 8,030,418, which ishereby incorporated by reference in its entirety. The hydroxylfunctionality remaining on the alkylphenol-aldehyde resin can also reactwith the epoxide too. Exemplary epoxide includes an epoxide of C₄-C₆₀α-olefin, for instance, a straight chain C₄-C₂₂ epoxide, or a straightchain C₆-C₁₆ epoxide.

An exemplary embodiment includes reacting an amine-modified in-situalkylphenol-aldehyde resin with an epoxide or a chemical reagent forstabilizing the amine moiety in the alkylphenol-aldehyde resin. Atypical amine used is morpholine.

Stabilization of Base-Modified Alkylphenol-Aldehyde Resin with aSalicylic acid

When preparing a base-modified alkylphenol-aldehyde resin, the in-situprocess may further comprise the step of reacting the base-modifiedalkylphenol-aldehyde resin with a salicylic acid. Typically, abase-modified alkylphenol-aldehyde resin needs to be reacted with anepoxide or other chemical reagents to stabilize the basic moiety orother reactive moieties in the modified resin. A detailed process forstabilizing a base-modified alkylphenol-aldehyde resin with an epoxidecan be found in U.S. Pat. No. 8,030,418, which is hereby incorporated byreference in its entirety. The hydroxyl functionality remaining on thealkylphenol-aldehyde resin reacts with the epoxide too. Exemplaryepoxide includes an epoxide of C₄-C₆₀ α-olefin, for instance, a straightchain C₄-C₂₂ epoxide, or a straight chain C₆-C₁₆ epoxide.

Using a salicylic acid in the process can eliminate the need to use anepoxide or other chemical reagents for stabilizing the basic moiety,thus providing a cost-effective alternative for stabilizing thebase-modified alkylphenol-aldehyde resin. The salicylic acid acts tostabilize the final resin by neutralizing any base such as amine (e.g.,morpholine) released. This is done by forming a salt that plasticizesthe resin, consequently diminishing the effects of molecular weightbuildup by the decomposition of salicylic acid to phenol. Thus, thebase-modified alkylphenol-aldehyde resin prepared by in-situ process,after reacting with a salicylic acid, can be completely stabilizedwithout using an epoxide or any other chemical reagents for stabilizingthe basic moiety.

The salicylic acid can be added to reaction system before or after thebase-modification reaction. The reactions may be carried outsequentially or simultaneously in a one-pot reaction vessel, or asseparate reactions isolating each or a desired intermediate product. Themodification and stabilization process are carried out in a reactor, forexample a customary vessel or glass flask which is equipped with astirrer, heater, thermostat, feeding device, reflux condenser and waterseparator.

Suitable salicylic acids include salicylic acid, its structuralderivatives, or mixtures thereof. A structural derivative of salicylicacid refers to a salicylic acid with one or more hydrogens on the phenolgroup of the salicylic acid being substituted with one or moresubstituents, The one or more substituents can be alkyl, alkoxy, phenylor substituted phenyl, alkenyl, halo, or acetyl. A detailed list ofstructural derivatives of salicylic acid, and the process of making themmay be found in U.S. Pat. Nos. 4,131,618 and 5,734,078, which are herebyincorporated by reference in their entirety. Typically, salicylic acid,alkyl salicylic acid (such as salicylic acid with one or more C₁-C₄alkyl groups substituted on the phenol group of the salicylic acid;e.g., 3,5-di-tert-butylsalicylic acid), alkoxy salicylic acid (such assalicylic acid with one or more C₁-C₄ alkoxy groups substituted on thephenol group of the salicylic acid), acetylsalicylic acid, orcombinations thereof, are used.

A further description of the process for preparing base-modifiedalkylphenol-aldehyde resin with improved stability with a salicylic acidmay be found in U.S. Provisional Application, entitled “ModifiedAlkylphenol-Aldehyde Resins Stabilized by a Salicylic Acid,” filed onAug. 29, 2013, which is hereby incorporated by reference in itsentirety.

In-Situ Alkylphenol-aldehyde Resin and Its Use in TackfierComposition/Rubber Composition

Another aspect of the invention relates to an alkylphenol-aldehyde resinprepared by reacting, without pre-purification, a raw alkylphenolcomposition directly with one or more aldehydes. The raw alkylphenolsource comprises one or more alkylphenol compounds and at least about 1wt % phenol. Each alkylphenol compound has one or more alkylsubstituents.

The in-situ alkylphenol-aldehyde resins includes resins resulted fromall the above embodiments of the in-situ process in preparing an in-situalkylphenol-aldehyde resin.

The resulting in-situ alkylphenol-aldehyde resin can be a novolak typeresin, as well as a resole type resin or a base-modified resole resin,depending on the manner in preparing the in-situ alkylphenol-aldehyderesin, as discussed in the above embodiments of the in-situ process.

The resulting in-situ alkylphenol-aldehyde resin can also be mixed withalkylphenol-aldehyde resins prepared from pure alkylphenol, including apure alkylphenol composition or a alkylphenol composition containingmixture of different pure alkylphenols.

Another aspect of this invention relates to a tackifier compositioncomprising the alkylphenol-aldehyde resin prepared by reacting, withoutpre-purification, a raw alkylphenol composition directly with one ormore aldehydes. The raw alkylphenol source comprises one or morealkylphenol compounds and at least about 1 wt % phenol. Each alkylphenolcompound has one or more alkyl substituents. The tackifier compositionhas improved tack performance.

The in-situ alkylphenol-aldehyde resins prepared from the in-situalkylphenol composition are useful to improve tack and tack retention,when used in a tackifier composition. The tackifier compositioncomprising the in-situ alkylphenol-aldehyde resin has consistently shownenhanced tack performance compared to the same tackifier compositioncomprising a regular alkylphenol-aldehyde resin prepared from a purifiedalkylphenol composition.

The tackifier composition may further comprise alkylphenol-aldehyderesins prepared from pure alkylphenol, including a pure alkylphenolcomposition or a alkylphenol composition containing mixture of differentpure alkylphenols.

Another aspect of this invention relates to a rubber compositioncomprising the alkylphenol-aldehyde resin prepared by reacting, withoutpre-purification, a raw alkylphenol composition directly with one ormore aldehydes. The raw alkylphenol source comprises one or morealkylphenol compounds and at least about 1 wt % phenol. Each alkylphenolcompound has one or more alkyl substituents. The rubber composition hasimproved tack performance. The rubber composition has also improvedprocessing performance.

The in-situ alkylphenol-aldehyde resins prepared from the in-situalkylphenol composition are useful to improve tack and tack retention ina rubber composition. The rubber composition comprising the in-situalkylphenol-aldehyde resin has consistently shown enhanced tackperformance compared to the same rubber composition comprising a regularalkylphenol-aldehyde resin prepared from a purified alkylphenolcomposition.

The in-situ alkylphenol-aldehyde resins prepared from the in-situalkylphenol composition are also useful to improve the processingperformance of a rubber composition. The rubber composition comprisingthe in-situ alkylphenol-aldehyde resin has consistently shown enhancedprocessing performance compared to the same rubber compositioncomprising a regular alkylphenol-aldehyde resin prepared from a purifiedalkylphenol composition.

A parameter to measure the processing performance (the performance ofrubber mixing process) of a rubber composition is viscosity.Heterogenous nature of rubber compounds, strong interaction betweenvarious components, and viscoelastic nature of elastomers and flowbehavior of such complex materials make the processing of rubbercompounds complex. If the viscosity of the rubber composition is toolow, it does not help with dispersing the additives such as fillers; onother than hand, if the viscosity of the rubber composition is too high,the rubber composition becomes very stiff, makes the mixing processdifficult and energy consuming. Controlling the amount of the in-situalkylphenol-aldehyde resins, the individual component and the relativeconcentration of the components in the in-situ alkylphenol-aldehyderesins in the rubber composition can modulate the viscosity of therubber composition, thus modulating the processibility of the rubbercomposition. Typically, the mooney viscosity is less than 100, or 80 forproperly processing the rubber.

The rubber composition may further comprise alkylphenol-aldehyde resinsprepared from pure alkylphenol, including a pure alkylphenol compositionor a alkylphenol composition containing mixture of different purealkylphenols.

The rubber composition comprises, besides the in-situalkylphenol-aldehyde resin, one or more rubber compounds. The rubbercompound includes a natural rubber, a synthetic rubber, or a mixturethereof. For instance, the rubber composition is a natural rubbercomposition.

Alternatively, the rubber composition can be a synthetic rubbercomposition. Representative synthetic rubbery polymers includediene-based synthetic rubbers, such as homopolymers of conjugated dienemonomers, and copolymers and terpolymers of the conjugated dienemonomers with monovinyl aromatic monomers and trienes. Exemplarydiene-based compounds include, but are not limited to, polyisoprene suchas 1,4-cis-polyisoprene and 3,4-polyisoprene; neoprene; polystyrene;polybutadiene; 1,2-vinyl-polybutadiene; butadiene-isoprene copolymer;butadiene-isoprene-styrene terpolymer; isoprene-styrene copolymer;styrene/isoprene/butadiene copolymers; styrene/isoprene copolymers;emulsion styrene-butadiene copolymer; solution styrene/butadienecopolymers; butyl rubber such as isobutylene rubber; ethylene/propylenecopolymers such as ethylene propylene diene monomer (EPDM); and blendsthereof. A rubber component, having a branched structure formed by useof a polyfunctional modifier such as tin tetrachloride, or amultifunctional monomer such as divinyl benzene, may also be used.Additional suitable rubber compounds include nitrile rubber,acrylonitrile-butadiene rubber (NBR), silicone rubber, thefluoroelastomers, ethylene acrylic rubber, ethylene vinyl acetatecopolymer (EVA), epichlorohydrin rubbers, chlorinated polyethylenerubbers such as chloroprene rubbers, chlorosulfonated polyethylenerubbers, hydrogenated nitrile rubber, hydrogenated isoprene-isobutylenerubbers, tetrafluoroethylene-propylene rubbers, and blends thereof.

The rubber composition can also be a blend of natural rubber with asynthetic rubber, a blend of different synthetic rubbers, or a blend ofnatural rubber with different synthetic rubbers. For instance, therubber composition can be a natural rubber/polybutadiene rubber blend, astyrene butadiene rubber-based blend, such as a styrene butadienerubber/natural rubber blend, or a styrene butadiene rubber/butadienerubber blend. When using a blend of rubber compounds, the blend ratiobetween different natural or synthetic rubbers can be flexible,depending on the properties desired for the rubber blend composition.

The in-situ alkylphenol-aldehyde resin may be added to a rubbercomposition in the same amount, in the same manner and for the same usesas other known tackifers. In one embodiment, in-situalkylphenol-aldehyde resin is used in an amount ranging from about 0.1per hundred rubber (phr) to 10 phr, for instance, from about 0.5 phr to10 phr, from about 1 phr to about 7 phr, from about 2 phr to about 6phr, or from about 1 phr to about 5 phr.

Also, the rubber composition may comprise additional materials, such asa methylene donor, one or more additives, one or more reinforcingmaterials, and one or more oils. As known to the skilled in the art,these additional materials are selected and commonly used inconventional amounts.

Suitable methylene donors include, for instance, hexamethylenetetramine(HMTA), di-, tri-, tetra-, penta-, or hexa-N-methylol-melamine or theirpartially or completely etherified or esterified derivatives, forexample hexamethoxymethylmelamine (HMMM), oxazolidine orN-methyl-1,3,5-dioxazine, and mixtures thereof.

Suitable additives include, for instance, sulfur, carbon black, zincoxides, silica, waxes, antioxidant, antiozonants, peptizing agents,fatty acids, stearates, accelerators, curing agents, activators,retarders, a cobalt, adhesion promoters, resins such as tackifyingresins, plasticizers, pigments, additional fillers, and mixturesthereof.

Suitable reinforcing materials include, for instance, nylon, rayon,polyester, aramid, glass, steel (brass, zinc or bronze plated), or otherorganic and inorganic compositions. These reinforcing materials may bein the form of, for instance, filaments, fibers, cords or fabrics.

Suitable oils include, for instance, mineral oils and naturally derivedoils. Examples of naturally derived oils include tall oil, linseed oil,and/or twig oil. Commercial examples of tall oil include, e.g., SYLFAT®FA-1 (Arizona Chemicals) and PAMAK 4® (Hercules Inc.). The one or moreoils may be contained in the rubber composition, relative to the totalweight of rubber compounds in the composition, less than about 5 wt %,for instance, less than about 2 wt %, less than about 1 wt %, less thanabout 0.6 wt %, less than about 0.4 wt %, less than about 0.3 wt %, orless than about 0.2 wt %. The presence of an oil in the rubbercomposition may aid in providing improved flexibility of the rubbercomposition after vulcanization.

The rubber compositions can be vulcanized by using mixing equipment andprocedures conventionally employed in the art. Likewise, the finalrubber products can be fabricated by using standard rubber curingtechniques. The reinforced rubber compounds can be cured in aconventional manner with known vulcanizing agents at about 0.1 to 10phr. A general disclosure of suitable vulcanizing agents may be found inKirk-Othmer, Encyclopedia of Chemical Technology (3rd ed., Wiley, NewYork, 1982) vol. 20, pp. 365 to 468 (particularly “Vulcanization Agentsand Auxiliary Materials,” pp. 390 to 402), and Vulcanization by A. Y.Coran, Encyclopedia of Polymer Science and Engineering (2nd ed., JohnWiley & Sons, Inc. 1989), both of which are incorporated herein byreference. Vulcanizing agents can be used alone or in combination.

The rubber compositions containing the in-situ alkylphenol-aldehyderesin exhibit significantly enhanced initial tack and tack retention,and thus can be useful to make a wide variety of products, for instance,tires or tire components such as sidewall, tread (or treadstock,subtread), carcass ply, body ply skim, wirecoat, beadfiller, or overlaycompounds for tires. Suitable products also include hoses, power belts,conveyor belts, printing rolls, rubber shoe heels, rubber shoe soles,rubber wringers, automobile floor mats, mud flaps for trucks, ball millliners, and weather strips.

EXAMPLES

The following examples are given as particular embodiments of theinvention and to demonstrate the practice and advantages thereof. It isto be understood that the examples are given by way of illustration andare not intended to limit the specification or the claims that follow inany manner.

Example 1 Preparation of In-Situ Para-Tert-Butylphenol (PTBP) ViaIsobutylene and Phenol

A 2-liter autoclave was charge with phenol (707.8 grams) and Amberlyst®15 (Dow, MI) (57.0 grams). The reactor was heated to 90-100° C. Thereactor was pressure-checked with nitrogen by venting and purging withnitrogen at 200 psi. The reactor was heated to 95° C., and, when thereactor temperature was stable, isobutylene (415.6 grams) was added tothe reactor at a controlled rate to ensure the reactor temperature doesnot exceed 100° C. Once the addition of isobutylene was completed, thereaction was maintained at 95° C. for 2 hours, and the reaction mixturewas sampled by the gas chromatography (GC) analysis. The reaction wasconsidered complete when the difference of a component in the samplecompared to that in the previous sample was within 0.5 wt % for allreaction components.

A typical product composition of in-situ PTBP prepared via isobutyleneand phenol is shown in Table 1.

TABLE 1 A Typical Product Composition of In-Situ PTBP Prepared viaIsobutylene and Phenol Phenol (wt %) 6.00-8.00 Butylphenol (wt %) >75.0Dialkylated phenol (wt %) <15.0 2,4,6-Tri-Tert-Butylphenol (wt %)  <0.5Water by Karl Fisher ^(a) <1000 ppm ^(a) The amount of water wasdetermined by Karl Fischer titration, which is a classic titrationmethod in analytical chemistry that uses coulometric or volumetrictitration to determine trace amounts of water in a sample.

Example 2 Preparation of In-Situ Para-Tert-Butylphenol (PTBP) ViaTransalkylation of PTBP Crude with Phenol

A 2-liter flask was charged with PTBP crude (620 grams), phenol (380grams) and Amberlyst® 15 (50 grams). The reaction was heated to 95° C.,and the temperature was maintained at 95° C. for 2 hours. The reactionmixture was sampled every hour. The reaction was considered completewhen the difference of a component in the sample compared to that in theprevious sample was within 0.5 wt % for all reaction components.

A typical product composition of in-situ PTBP prepared viatransalkylation of PTBP crude with phenol is shown in Table 2.

TABLE 2 A Typical Product Composition of In-Situ PTBP prepared viaTransalkylation of PTBP Crude with Phenol Phenol (wt %) 6.00-8.00Butylphenol (wt %) >75.0 Dialkylated phenol (wt %) <15.02,4,6-Tri-Tert-Butylphenol (wt %)  <0.5 Water by Karl Fisher ^(a) <1000ppm ^(a) The amount of water was determined by Karl Fischer titration,which is a classic titration method in analytical chemistry that usescoulometric or volumetric titration to determine trace amounts of waterin a sample.

The composition of the PTBP crude varies. The amount of each componentin the PTBP crude can be calculated and adjusted accordingly to achievea desired isobutylene/phenol mole ratio in the in-situ PTBP product.

Example 3 Preparation of In-Situ Mixture of Alkylphenols (PTBP andPara-Tert-Octylphenol (PTOP))

A 2-liter flask was charged with Amberlyst® 15 (45.2 grams) and phenol(1000 grams). The temperature of reactor was set to 80° C. and theagitation was turned on. Isobutylene (380.2 grams) was added over aperiod of 1.5-2 hours. Diisobutylene (420.8 grams) was then added over aperiod of 6-8 hours. After the additions were complete, the mixture wasthen allowed to equilibrate for 1-2 hours. After another one hour, thebatch was sampled for analysis. Once the reaction product was determinedto be within specifications, the product was transferred as soon aspossible to a storage vessel.

The typical weight ratios of different reagents in a standard load isshown in Table 3, and a typical product assay is shown in Table 4.

TABLE 3 Weight Ratios of Reagents in a Standard Load Amberlyst ® 15CATALYST 4.52 Phenol 100.00 Diisobutylene 42.83 Isobutylene 38.20

TABLE 4 Typical Product Assay Showing Products in Weight Ratios DiTOP5.12 Light Ends 0.20 Phenol 1.58 PTBP 57.76 PTOP including two isomers32.98 2,4-DiTOP 4.20

Example 4 Preparation of Alkylphenol-Aldehyde Resin from Mixed In-SituAlkylphenol (In-Situ PTOP and In-Situ PTBP) (Resin ii-1)

The resin kettle was set for reflux return, and water (600 kg, 33.3kilomoles) was loaded to the azeo receiver. Molten mixture of in-situPTBP and in-situ PTOP (42,000 kg, 241.4 kilomoles) was pumped to thekettle with the agitator turned on after 1000 kg of the molten mixturewas loaded. When all in-situ monomers were loaded, xylene (1000 kg, 9.4kilomoles) was charged to the reactor. Dodecylbenzene sulfonic acid (60kg, 0.19 kilomoles) was then transferred into the resin kettle and mixedwith the molten in-situ monomer solution. The batch temperature was thenadjusted to 125-130° C., and the kettle was set for reactiondistillation which would send the overhead condensation liquid into theazeo receiver, as described in the next step when formaldehyde would beadded. The overhead condensation liquid would contain water, xylene,unreacted formaldeyde and some phenolic compounds. The azeo would fillwith xylene accumulating as the top layer which could return to thekettle. The bottom layer would contain mostly water and would be drawnoff from the azeo receiver, and sent to a collection tank during theprocess.

Using a subsurface addition system, 50% aqueous formaldehyde (12,600 kg,210 kilomoles) was metered into the reaction batch at a sufficientlyslow rate to establish an exotherm; once the exotherm was established,the addition rate was increased until 5/liths of the formaldehyde wasadded. The addition rate was decreased to maintain reaction efficiencyas the condensation product viscosity increased. Throughout the additionof the formaldehyde, the batch temperature was maintained at 125-135° C.The level of unreacted formaldehyde in the overhead stream could bemonitored during the course of the reaction. After the formaldehydeaddition was completed, the product melt point was estimated using avacuum-oven melt point technique. The target melt point was 125-130° C.If the melt point is low, formaldehyde can be added to increase the meltpoint. When the melt point of the product reached the desired range, theproduct was neutralized by adding 85% triethanolamine (45 kg 0.30kilomoles).

The resin kettle was then set for total distillation, and the reactorwas heated under atmospheric pressure to 160° C. Once the temperaturereached 160° C., full vacuum was applied slowly, and the reaction batchwas distilled under vacuum to 170-180° C., and this condition was heldfor 15 minutes. After 15 minutes, the melt point was checked with aring-and-ball test. When the melt point of the product reached thedesired specification, the molten resin was transferred to a coolingsystem for final packing as solid resin flakes or pastilles (42,250 kg,95% yield).

Characterization of the product in this example: Softening pointspecification: 120-140° C. (e.g., lot 2201-198: 132.8° C.); Gelpermeation chromatography (GPC): Molecular Weight (Mw) was 1450-2175,Number Average Molecular Weight (Mn) was 910-1380; Differential Scanningcalorimetry (DSC): Glass transition Temperatures (T_(g)) was 90-95° C.;Fourier Transform Infrared Spectroscopy (FTIR): 3227 cm⁻¹ (50% T,broad), 2956 cm⁻¹ (20% T, sharp), 1755 cm⁻¹ (80% T, broad), 1605 cm⁻¹(75% T, broad), 1485 cm⁻¹ (30% T, sharp), 1363 cm⁻¹ (45% T, sharp), 1205cm⁻¹ (45% T, sharp), 1125 cm⁻¹ (67% T, sharp), 875 cm⁻¹ (75% T sharp),819 cm⁻¹ (65% T, sharp). Weight % free monomers in resin: 0.05-0.3%xylene, 0.05-0.5% PTBP, 0.3-1.0% PTOP. Melt viscosity at 180° C. was900-1000 cPs. Acid number was 24-55.

The resin prepared by this method presented excellent thermal stabilityeven after 30 hours at 180° C.

Example 5 Preparation of Alkylphenol-Aldehyde Resin from Mixed In-SituAlkylphenol (In-Situ PTOP and In-Situ PTBP) (Resin ii-2)

Following the same reaction procedures as described in Example 4, ahigher melt-point resin was prepared where the target ball and ring meltpoint of the desired product was ranging from 130° C. to 140° C., forinstance, 135° C. When the melt point of the product reached the desiredspecification (i.e., a ball and ring softening point of at least130-140° C., for instance, 135° C.), the molten resin was transferred toa cooling system for final packing as solid resin flakes or pastilles(42,362 kg, 95% yield).

Example 6 Preparation of Alkylphenol-Aldehyde Resin from Mixed In-SituAlkylphenol (In-Situ PTOP and In-Situ PTBP) (Resin ii-3)

Using the same reaction procedures as described in Example 4, a highermelt point resin was prepared where the target ball and ring melt pointof the desired product was ranging from 135 to 145° C., for instance,140° C. With the melt point of the product reached the desiredspecification (i.e., a ball-and-ring softening point of at least135-145° C., for instance, 140° C.), the molten resin was transferred toa cooling system for final packing as solid resin flakes or pastilles(42,630 kg, 95% yield).

Example 7 Tack Application Testing for Alkylphenol-Aldehyde ResinPrepared from Mixed In-Situ Alkylphenol Composition

In-situ alkylphenol-aldehyde resins prepared from mixed in-situalkylphenol composition according to Example 4 was blended in a 60/40natural rubber/polybutadiene (NR/PBD) rubber blend at 4 phr, and theresulted rubber blended were tested for tack performance. The tackresults are shown in FIG. 1.

FIG. 1 shows the tack performance (tack and tack retention) of therubber blends using the mixed in-situ resin prepared from a mixture ofin-situ PTBP and in-situ PTOP (Resin ii-1), as compared to the tackperformance of the rubber blends using in-situ PTOP resin (Resini-PTOP), and the tack performance of the rubber blends using resinsprepared from a mixture of in-situ PTOP and resin-grade PTBP (Resinir-1). Overall, FIG. 1 shows that the tack results from the mixedin-situ PTBP/PTOP resins (Resin ii-1) exceeded tack results from thein-situ PTOP resin (Resin i-PTOP), and the tack results from the mixedin-situ PTBP/PTOP resins (Resin ii-1) exceeded the tack results from themixture of resin-grade PTBP and in-situ PTOP (Resin ir-1)

Example 8 Preparation of In-Situ Alkylphenol Resin from In-SituAlkylphenol (in-situ PTBP) (Resin i-PTBP)

The reaction system was set for atmospheric azeotropic distillation, thedistillation receiver was filled to 90% capacity with water, and theresin kettle was pre-heated to 100° C. Molten in-situ butylphenol (19051kg, 126.82 kilomols) was charged into the kettle. Xylene (1360 kg, 2.4%of the in-situ butylphenol load) was charged into the batch and agitateduntil a homogenous solution was obtained. Dodecylbenzene sulfonic acid(74 kg, 0.226 kilomoles) was then transferred into the kettle and mixedto the molten in-situ butylphenol solution. The batch temperature isthen adjusted to 130° C.

Using a subsurface addition system, 50% aqueous formaldehyde (6130 kg,102.07 kilomoles, F/P 0.805) is metered into the batch at a sufficientlyslow rate to maintain the reaction temperate at 120-130° C. The xylenelayer in the distillation receiver was returned to the batch whilecontinuously removing the water of the reaction. After the addition wascompleted, the reflux was maintained by heating the batch until theformaldehyde level in the reflux return was less than 1 wt %. The resinwas sampled for a ball and ring soften point of 130-135° C.Post-additions of formaldehyde could be performed to adjust thesoftening point higher. When the resin softening point was achieved,triethanolamine (44 kg, 0.29 kilomoles) was injected into the batch toneutralize the acid catalyst. Most of the xylene was thenatmospherically distilled off until the reaction temperature reached160° C. The remaining xylene was removed using vacuum distillation to amaximum of temperature of 180° C. and 0.1 atm. The kettle wasrepressurized with nitrogen and the resin was sampled to obtain aball-and-ring softening point of 133° C. and free PTBP of less than 5 wt%. At this point, the molten resin was transferred to a cooling systemfor final packing as solid resin flakes or pastilles. This processproduced Resin i-PTBP-2.

Lowering the melting point of the final product or adding lessformaldehyde during the process can produce Resin i-PTBP-1 (same in-situPTBP resin, but having a lower melting point than Resin i-PTBP-2).

In-situ alkylphenol-aldehyde resin (Resin i-PTBP-1 and Resin i-PTBP-2)prepared above were blended in a 60/40 natural rubber/polybutadiene(NR/PBD) rubber blend at 4 phr, and the resulted rubber blended weretested for tack performance. FIG. 2 shows the tack performance (tack andtack retention) of the rubber blends using the two in-situ PTBP resinshaving different melting points (Resin i-PTBP-1 and Resin i-PTBP-2), ascompared to the tack performance of the rubber blends usingcorresponding resin-grade PTBP resin (Resin r-PTBP-1 and Resinr-PTBP-2), and the tack performance of the rubber blends using resinsprepared from a mixture of in-situ PTOP and in-situ PTBP (Resin ii-1).

As shown in FIG. 2, the tack results from both the in-situ PTBP resins(Resin i-PTBP-1 and Resin i-PTBP-2) exceeded the tack results from thecorresponding resin-grade PTBP resins (Resin r-PTBP-1 and Resinr-PTBP-2). Additionally, FIG. 2 shows that, overall, the tack resultfrom the mixed in-situ PTBP/PTOP resins (Resin ii-1) exceeded the tackresults from the in-situ PTBP resin with a lower melting point (Resini-PTBP-1).

Example 9 Preparation of Amine-Modified Alkylphenol-Aldehyde Resin fromIn-Situ Alkylphenol (In-Situ PTBP) and Stabilized by Salicylic Acid(Resin-i-PTBP-Amine-SA)

The resin kettle was set for reflux return, and pre-heated to 100° C.Molten in-situ butyl phenol (14515 kg, 96.63 kilomols) was charged to akettle. Dodecylbenzene sulfonic acid (27.2 kg, 0.08336 kilomoles) wasthen transferred into the kettle and mixed into the molten in-situ butylphenol. Using a powder transfer system, salicylic acid (725.75 kg, 5.25kilomoles) was added to the batch, agitated for sufficient time to makea homogeneous mixture. The batch temperature was then adjusted to 95° C.Using a subsurface addition system, 50% aqueous formaldehyde (4173 kg,69.48 kilomoles) was metered into the batch at a sufficiently slow rateto maintain the batch temperature at 90-98° C. After the addition wascompleted, reflux was maintained by heating the batch to 102° C. untilthe formaldehyde level in the reflux return was less than 2 wt %. Thebatch was then adjusted to 93° C., and xylene (1360 kg, 9 wt % of thein-situ butyl phenol load) was charged into the batch, and agitateduntil a homogenous solution was obtained.

Morpholine (1161 kg, 13.33 kilomoles) was pumped into the batch andagitated until a homogenous solution was obtained. Using a subsurfaceaddition system, 50% aqueous formaldehyde (1311 kg, 21.83 kilomoles) wasmetered into the batch at a slow enough rate so as to keep the batchtemperate at 90-98° C. After the addition was completed, the reflux wasmaintained by heating the batch to 102° C. until the formaldehyde levelin the reflux return was less than 0.2 wt %. Azeotropic distillation wasperformed to remove the water by heating the batch to 160° C. Once waterwas removed, vacuum distillation was performed by heating the batch to amaximum of 170° C. and 0.1 atm, and this condition was held withagitation for one hour. The kettle was then pressurized with nitrogen.Under distillation conditions, the molten resin was heated to 180° C.,and agitated until a ball and ring softening point of at least 133° C.and a free para-tert-butylphenol of less than 5 wt % were obtained. Atthis point, the molten resin was transferred to a cooling system forfinal packing as solid resin flakes or pastilles (17424 kg, 98% yield).

Characterization of the product in this example: Softening point133-143° C.; GPC: Mw 2186-3656, Mn 862-1020; DSC: Tg 83-87° C.; FTIR:3247 cm⁻¹ (50% Y, broad), 2960 cm⁻¹ (20% T, sharp), 1755 cm⁻¹ (80% T,broad), 1605 cm⁻¹ (75% T, broad), 1484 cm⁻¹ (30% T, sharp), 1362 cm⁻¹(45% T, sharp), 1205 cm⁻¹ (45% T, sharp), 1120 cm⁻¹ (67% T, sharp), 819cm⁻¹ (65% T, sharp). Weight % free monomers in resin: 1.5-3% morpholine,0.05-0.7% xylene, 3.5-5% PTBP, 0.47-1% DTBP, 0.07-0.38% phenol. Meltviscosity at 180° C. was 600-800 cPs. Acid number: 47-57.

In-situ amine-modified alkylphenol-aldehyde resin amine-modifiedprepared above (Resin i-PTBP-amine-SA) was blended in a 60/40 naturalrubber/polybutadiene (NR/PBD) rubber blend at 4 phr, and the resultedrubber blended were tested for tack performance. FIG. 3 shows theresults of tack and tack retention of rubber blends using an in-situresin prepared from in-situ PTBP with an amine modification and asalicylic-acid stabilization (Resin i-PTBP-amine-SA), as compared to thetack and tack retention of the rubber blends using in-situ PTBP resinswith a lower melting point (Resin i-PTBP-1), and the tack and tackretention of the rubber blends using resin-grade PTBP resin with a lowermelting point (Resin r-PTBP-1).

As shown in FIG. 3, the tack results from the amine-modified in-situPTBP resins stabilized by salicylic acid (Resin i-PTBP-amine-SA) werebetter than the tack results from the in-situ PTBP resins with a lowermelting point (Resin i-PTBP-1) and the resin-grade PTBP resin with alower melting point (Resin r-PTBP-1).

Example 10 Viscosity Comparison of In-Situ Alkylphenols (in-situ PTBP)(resin PTBP-i) and Resin-Grade Alkylphenols (Resin-Grade PTBP) (ResinPTBP-r)

In-situ alkylphenol-aldehyde resin was prepared according to proceduressimilar to those described in Examples 1-2, resulting in-situ PTBP(resin PTBP-i). Resin PTBP-i was blended in a 60/40 naturalrubber/polybutadiene (NR/PBD) rubber blend, and the mixing viscosity wastested. A control experiment was carried out on a resin-gradealkylphenols (resin PTBP-r), in which the same amount of resin PTBP-rwas blended in the same 60/40 natural rubber/polybutadiene (NR/PBD)rubber blend, and the mixing viscosity was tested. The results ofviscosity comparison are listed in Table 5.

As shown in Table 5, the differences in viscosity between in-situ PTBPand resin-grade PTBP are quite significant in various temperaturelevels.

TABLE 5 Viscosity Comparison of PTBP-i and PTBP-r PTBP-i PTBP-r T (° C.)cP ^(a) T cP 170 EEEE ^(b) 170 890 180 EEEE   180 240 190 8000 190 154200 3600 200 84 210  80 210 50 ^(a) cP is centaPoise or Pa*s(pascal*second); ^(b) EEEE means above the measurable range of theinstrument.

Although preferred embodiments have been depicted and described indetail herein, it will be apparent to those skilled in the art thatvarious modifications, additions, substitutions, and the like can bemade without departing from the spirit of the invention and these aretherefore considered to be within the scope of the invention as definedin the claims which follow.

We claim:
 1. An in-situ process for preparing an alkylphenol-aldehyderesin, comprising: providing a raw alkylphenol composition comprising:one or more alkylphenol compounds, each compound having one or morealkyl substituents, and at least about 1 wt % phenol; and reacting,without pre-purification, the raw alkylphenol composition directly withone or more aldehydes to form an in-situ alkylphenol-aldehyde resin. 2.The process of claim 1, wherein the alkylphenol composition includes apara-alkylphenol.
 3. The process of claim 2, wherein the alkylphenolcomposition includes para-tert-butylphenol.
 4. The process of claim 1,wherein the alkylphenol composition comprises para-tert-butylphenol,phenol, di-tert-butylphenol, and optionally tri-tert-butylphenol andortho-tert-butylphenol.
 5. The process of claim 1, wherein thealkylphenol composition comprises: about 50 to about 85 wt %para-tert-butylphenol, about 5 to about 10 wt % phenol, about 7 to about14 wt % di-tert-butylphenol, 0 to about 3 wt % ortho-tert-butylphenol,and 0 to about 1 wt % tri-tert-butylphenol.
 6. The process of claim 1,wherein the aldehyde is formaldehyde.
 7. The process of claim 1, whereinthe alkylphenol composition includes para-tert-butyl phenol andpara-tert-octylphenol.
 8. The process of claim 1, wherein thealkylphenol composition comprises para-tert-butylphenol,para-tert-octylphenol, phenol, di-tert-octylphenol, and optionallyortho-tert-octylphenol and tri-tert-octylphenol.
 9. The process of claim1, wherein the alkylphenol composition comprises para-tert-butylphenol,phenol, di-tert-butylphenol, optionally tri-tert-butylphenol andortho-tert-butylphenol, para-tert-octylphenol, di-tert-octylphenol, andoptionally ortho-tert-octylphenol and tri-tert-octylphenol.
 10. Theprocess of claim 1, wherein the tack performance of the formed in-situalkylphenol-aldehyde resin, when used in a rubber composition, increasesabout 10% or more compared to an alkylphenol-aldehyde resin preparedfrom a purified alkylphenol.
 11. The process of claim 10, wherein thepurified alkylphenol contains at least about 99% para-tert-butylphenolor at least about 99% para-tert-octylphenol.
 12. The process of claim10, wherein the purified alkylphenol contains less than about 1% phenol.13. The process of claim 10, wherein the tack retention of the formedin-situ alkylphenol-aldehyde resin increases about 40% or more.
 14. Analkylphenol-aldehyde resin prepared by reacting, withoutpre-purification, a raw alkylphenol composition directly with one ormore aldehydes, wherein the raw alkylphenol source comprises one or morealkylphenol compounds, each compound having one or more alkylsubstituents, and at least about 1 wt % phenol.
 15. Thealkylphenol-aldehyde resin of claim 14, wherein the alkylphenol-aldehyderesin is a novolak type resin.
 16. The alkylphenol-aldehyde resin ofclaim 14, wherein the alkylphenol-aldehyde resin is a resole type resin.17. The alkylphenol-aldehyde resin of claim 14, further comprisingalkylphenol-aldehyde resins prepared from pure alkylphenol.
 18. Atackifier composition having improved tack performance, when used in arubber composition, comprising the alkylphenol-aldehyde resin of claim14.
 19. The tackifier composition of claim 18, wherein the tackperformance of the formed in-situ alkylphenol-aldehyde resin increasesabout 10% or more compared to a tackifier composition comprising analkylphenol-aldehyde resin prepared from a purified alkylphenol.
 20. Thetackifier composition of claim 19, wherein the tack retention of theformed in-situ alkylphenol-aldehyde resin increases about 40% or more.21. A rubber composition comprising: the alkylphenol-aldehyde resin ofclaim 14, and a natural rubber, a synthetic rubber, or a mixturethereof.
 22. The rubber composition of claim 21, wherein the in-situalkylphenol-aldehyde resin is used in an amount ranging from about 1 phrto about 7 phr.
 23. The rubber composition of claim 21, furthercomprising alkylphenol-aldehyde resins prepared from pure alkylphenol.24. A tire comprising the rubber composition of claim
 21. 25. Theprocess of claim 1, further comprising the step of reacting thealkylphenol-aldehyde resin with an amine, forming an amine-modifiedalkylphenol-aldehyde resin.
 26. The process of claim 25, furthercomprising the step of reacting the amine-modified alkylphenol-aldehyderesin with an epoxide or a chemical reagent for stabilizing the aminemoiety in the alkylphenol-aldehyde resin.
 27. The process of claim 25,further comprising the step of reacting the amine-modifiedalkylphenol-aldehyde resin with a salicylic acid.
 28. The process ofclaim 27, wherein the amine is morpholine.